Calcium-aluminum system hydrogen absorbing alloy

ABSTRACT

The calcium-aluminum system hydrogen absorbing alloy of the present invention is an alloy which is composed of a mixture P of Ca with Mg and an Al base alloy Q, has a molar ratio P:Q of 1:1.5 to 2.8 and shows a Laves phase with the C15-type structure as the fundamental structure thereof.

This is a continuation of application Ser. No. 08/495,744 filed Jun. 27,1995, now U.S. Pat. No. 5,656,105.

BACKGROUND

This invention relates to calcium-aluminum system hydrogen absorbingalloys.

Hydrogen absorbing alloys are characterized by reacting directly withhydrogen and thus quickly absorbing a large amount of hydrogen, whiledesorbing the hydrogen thus absorbed. Accordingly, they enablereversible absorption and desorption of hydrogen. Thus there have beenactively made developments regarding techniques in the use of thesehydrogen absorbing alloys mainly in the field of energetic technology.Hydrogen absorbing alloys are being applied to various purposesincluding the storage and transport of hydrogen, energy conversion mediaand negative electrodes for some secondary batteries.

In order to put a hydrogen absorbing alloy into practical use, it isgenerally necessary that the hydrogen absorbing alloy satisfy thefollowing requirements.

(1) Having such a hydrogen absorption pressure and a hydrogendissociation pressure as to facilitate handling within the operatingtemperature range.

(2) Showing high rates of hydrogen sorption within the operatingtemperature range.

(3) Having a large chargeable hydrogen capacity within the operatingtemperature range and under such a pressure as to facilitate handling.

(4) Being easily activated during initial hydriding.

(5) Showing a small difference between hydrogen pressures required forhydrogen absorption and hydrogen desorption (i.e., hysteresis).

(6) Being highly durable when subjected to repeated absorption anddesorption over a long period of time.

(7) The cost of materials being low.

(8) The alloy per se being not heavy.

Regarding these points, there have been publicly known Laves phasehydrogen absorbing alloys with the C15-type structure such as group IVametal-3d transition metal system alloys (Ti--Cr system, Zr--V system,Zr--Mn system, etc.) and rare earth metal-3d transition metal systemalloys La--Ni system, Mm (misch metal)-Ni system, etc.!.

On the other hand, publicly known hydrogen absorbing alloys containingCa as the main component are exemplified by Ca--Ni system and Mg--Casystem alloys. Although the Ca--Ni system alloy has a large hydrogenstorage capacity and can easily undergo the initial activation, itrequires a large amount of Ni which is an expensive and heavy element.Although the Mg--Ca system alloy is a light one, it has not been putinto practical use because it suffers from some problems, i.e., (a)requiring prolonged initial activation at a high temperature; (b) havinga low equilibrium hydrogen dissociation pressure at ordinarytemperatures; and (c) being poor in oxidation resistance.

Therefore attempts have been made to impart the characteristics (1) to(8) as described above to a hydrogen absorbing alloy or to improve thesecharacteristics to thereby give a hydrogen absorbing alloy having animproved practical availability by, for example, making the compositionratio of a hydrogen absorbing alloy (mainly the above-mentioned Lavesphase hydrogen absorbing alloy or one containing Ca as the maincomponent) nonstoichiometric or making multi-components. In the case ofCa--Ni system or Mg--Ca system alloys, for example, attempts have beenmade to replace some part of the alkaline-earth metal with a rare earthelement or to replace some part of Ni with other transition elements,etc.

When used in products such as negative electrodes of nickel-metalhydride (Ni--MH) secondary batteries or fuel cells, however, thesealloys are undesirable from the viewpoints of lightness and cheapness.Thus they leave much room for improvement regarding these points.

SUMMARY

Accordingly, it is a primary object of the present invention to providea hydrogen absorbing alloy which has practically usable hydrogensorption characteristics and is excellent in lightness and cheapness.

In order to achieve the above-mentioned object, the present inventorshave conducted extensive studies. As a result, they have successfullyfound that Laves phase alloys with the C15-type structure, which arecomposed of a Ca base material and an Al base alloy at a specific molarratio, have practically usable hydrogen sorption characteristics and arehighly advantageous from the viewpoints of lightness and cheapness. Thepresent invention has been completed based on this finding.

Thus, the gist of the present invention resides in a calcium-aluminumsystem hydrogen absorbing alloy, which is an alloy composed of a mixtureP of Ca with Mg and an Al base alloy Q, characterized in that the molarratio P:Q is 1:1.5 to 2.8 and it is fundamentally Laves phase with theC15-type structure.

THE DRAWINGS

FIG. 1(a) is a calcium-aluminum system binary phase diagram, while FIG.1 (b) is an aluminum-boron system binary phase diagram;

FIG. 2(a) is a diagram showing differential thermal analysis curves ofpowdery alloys Ca₁₋α Mg.sub.α (Al₁₋β M.sub.β)₂, while FIG. 2(b) is adiagram showing the heat history of these powdery alloys during themeasurement;

FIG. 3 shows the X-ray diffraction patterns of each calcium-aluminumsystem hydrogen absorbing alloys, Ca(Al₁₋γ B.sub.γ)₂, of the presentinvention;

FIG. 4 shows the X-ray diffraction patterns of each calcium-aluminumsystem hydrogen absorbing alloys, Ca₁₋α Mg.sub.α (Al₁₋β M.sub.β)₂ of thepresent invention;

FIG. 5 is a diagram showing the hydrogenpressure-composition-temperature (p-c-T) characteristic curves ofCa--Al(--M) system alloys; and

FIG. 6(a) is a diagram showing the p-c-T curves of an alloy CaAl₁.8 B₀.2at 0° to 60° C., while FIG. 6(b) is a diagram showing the p-c-T curvesat 60° C. formed by using γ as a parameter against Ca(Al₁₋γ B.sub.γ)₂.

THE PREFERRED EMBODIMENTS

In the hydrogen absorbing alloy of the present invention, the molarratio of the mixture P to the aluminum base alloy Q (P:Q) usually fallswithin a range of 1:1.5 to 2.8. It is not preferable that the molarratio is outside the range as specified above, since the hydrogenstorage capacity is largely reduced and thus the hydrogen absorbingalloy fails to fully exert its function in such a case. The hydrogenabsorbing alloy of the present invention has the Laves phase with theC15-type structure as its fundamental structure. It is desirable thatthe Laves phase with the C15-type structure amounts at least to 70% byvolume in the alloy. It is not preferable that the proportion of theLaves phase with the C15-type structure is lowered (i.e., structureswith different phases are deposited in a large amount). This is becausethe crystallinity of the Laves phase with the C15-type structure isrelatively deteriorated and thus the hydrogen storage capacity of thealloy is lowered in this case.

In the above-mentioned mixture P, some part of Ca has been replaced withMg. The replacement with Mg is particularly effective in lightening thealloy. From this point of view, it is preferable that the mixture P isone represented by the general formula (1-α)Ca+60 Mg (wherein 0<α≦0.2).It is not preferable that a exceed 0.2, since there is a risk that analloy of constant qualities cannot be produced at a high reproducibilityor the Laves phase with the C15-type structure cannot be achieved whilestructures with different phases are deposited in an elevated amount insuch a case. A smaller value of α results in a lower contribution to thelightening of the alloy. In the case where the lightness of the alloy isnot particularly required, however, the value α may be an extremelysmall one or even 0 (i.e., Ca is used alone).

The alloy composition of the aluminum base alloy Q may be arbitrarilyselected depending on, for example, the composition of theabove-mentioned mixture P and the purpose of the utilization of thehydrogen absorbing alloy. In usual cases, it is preferable to use onerepresented by the general formula Al₁₋β M.sub.β (wherein 0<β≦0.3, theelement M means at least one element selected from among boron, carbon,silicon, germanium, tin, lead, titanium, vanadium, chromium, manganese,iron, cobalt, nickel, copper and zinc). It is not preferable that βexceed 0.3. This is because, in such a case, an element having a highmelting point is not molten but remains as such and thus there is a riskthat an alloy of constant qualities cannot be produced at a highreproducibility or the Laves phase with the C15-type structure cannot beachieved while structures with different phases are deposited in anelevated amount. The value β may be an extremely small one or even 0(i.e., Al is used alone), so long as the homogenization of the moltensolution in the preparation of the alloy and the improvement in thehydrogen absorption characteristics of the resulting alloy are notdeteriorated thereby.

In the present invention, use can be made of an alloy represented by thegeneral formula Al₁₋γ B.sub.γ (wherein 0<γ≦0.5) as the aluminum basealloy Q. That is to say, an improved lightness can be imparted to thealloy by replacing some part of aluminum with boron. It is notpreferable that γ exceed 0.5. This is because, in such a case, thereproducibility of the alloy is lowered and crystals of structures withdifferent phases are deposited in a large amount, like in theabove-mentioned case.

The calcium-aluminum system hydrogen absorbing alloy of the presentinvention may be produced in the same manner as the publicly knownmethod for producing a hydrogen absorbing alloy with the use of startingmaterials which have been prepared in the composition as describedabove. In the case of a calcium-aluminum system hydrogen absorbing alloywherein a single phase can be hardly formed merely by directly effectingradio-frequency induced melting, the alloy of the present inventionhaving the desired hydrogen absorption characteristics can be easilyobtained by preliminarily preparing an alloy with partial substitutionof aluminum by an arc melting method as an initial step or preliminarilysubstituting some part of calcium with magnesium.

When aluminum is substituted with boron, for example, a binary alloyAl₁₋γ B.sub.γ having a melting point of about 660° to 1,500° C. isobtained FIGS. 1(a) and (b)!. It is often effective to synthesize Al₁₋γB.sub.γ before forming CaAl₂ system alloy because of the following. Whenthe raw materials(Ca and Al) are heated up, pure Al with the low meltingpoint is melted first, because raw aluminum has a lower melting pointthan calcium. When the materials are further heated up, calcium withhigh melting point and vapor pressure begins bumping, then gaseouscalcium often blows off surrounding melting Al. Thus the formation ofhomogenous alloy with the prepared composition is sometimes prevented.However, by using the Al₁₋γ B.sub.γ alloy with higher melting point thanCa instead of only Al, Ca seldom bumps explosively (in our experience).In this case, B causes segregation in CaAl₂ or forms a solid solutionwith the matrix CaAl₂ as a substitutional or interstitial atom, whichcontributes also to the improvement in the hydriding properties of thealloy.

EXAMPLES

To further clarify the characteristics of the present invention, thefollowing Examples will be given. In these Examples, analyses werecarried out each in the following manner.

(1) Differential thermal analysis (DTA):

Use was made of about 20 mg of each alloy powder and the analysis waseffected in a hydrogen gas (H₂) atmosphere of 5 MPa within a temperaturerange of from ordinary temperature to 500° C. A comparison among theX-ray diffraction patterns obtained at the temperatures (A), (B) and (C)in FIG. 2(a) indicates that the peak in the lower temperature region (ataround 330° C.) shows a primary hydrogenation of the alloy, while theone in the higher temperature region (at around 430° C.) shows furtherhydrogenation of the formed hydride.

(2) X-ray powder diffractometry (XRD):

Use was made of the θ-2θ method. It has been thus confirmed that thealloy of the present invention fundamentally has the Laves phase withthe C15-type structure.

(3) Determination of p-c-T (hydrogen pressure-composition-temperature)characteristics:

By using an automated Sieverts'-type apparatus, about 300 mg of an alloypowder was sealed in a stainless reaction vessel and activated followedby the determination in a hydrogen atmosphere within a range of from 1kPa to 3.3 MPa. The initial activation was carried out in the followingmanner by reference to the results of the differential thermal analysis.Namely, the sample was heated up to 350° C. After evacuation(by a rotarypump), H₂ of 3.5 MPa was introduced thereinto. The sample was exposed tohydrogen at this pressure for 150 minutes and then cooled to roomtemperature to thereby allow the alloy to absorb H₂.

Example 1

Commercially available Ca and Al were weighed to give a molar ratio ofCa:Al of 1:2 and were melted to thereby give an alloy CaAl₂. The samplethus obtained was subjected to DTA, XRD and the determination of thep-c-T characteristics. The results are given in Table 1, FIGS. 2(a) and(b), FIG. 3 and FIG. 5. The CaAl₂ thus prepared had the Laves phase withthe C15-type structure with a lattice constant (a) of 0.80793 (nm).

                  TABLE 1                                                         ______________________________________                                                        Molecular                                                     Chemical formula of alloy                                                                     weight       H/M                                              ______________________________________                                        CaAl.sub.1.8 B.sub.0.2                                                                        90.809       0.24 (60° C.)                             LaNi.sub.5      432.46       1.00 (20° C.)                             TiFe            103.747      0.95 (40° C.)                             TiMn.sub.1.5    130.307      0.96 (20° C.)                             CaNi.sub.5      333.63       0.67 (30° C.)                             CaMg.sub.2      88.704       1.24 (320° C.)                            Mg.sub.2 Ni     107.334      1.33 (250° C.)                            ______________________________________                                         Note: a comparison of publicly known hydrogen absorbing alloys with the       one of the present invention.                                            

Example 2

Al and Ni or Sn employed as a substituent for Al (hereinafter referredto as M) were weighed to give a molar ratio of Al:M of (1-β):β andmelted to thereby give an alloy Al₁₋β M.sub.β (alloy A). This alloy Aand Ca were weighed to give a molar ratio of Ca:alloy A of 1:δ(1.5≦δ≦2.8) and melted again to give two alloys Ca(Al₁₋β M.sub.β).sub.δ,i.e., CaAl₂ Ni₀.8 and CaAl₁.8 Sn₀.2. These samples were evaluated in thesame manner as the one of Example 1. FIG. 5 shows the p-c-Tcharacteristics of CaAl₁.8 Sn₀.2, CaAl₂ Ni₀.8 and CaAl₁.8 Ni₀.2.

In FIGS. 5 and 6, the abscissa refers to the hydrogen storage capacityH/M, while the ordinate refers to the equilibrium hydrogen dissociationpressure P (MPa).

The term "hydrogen storage capacity H/M" as used herein refers to theratio of the hydrogen atom number H to the atom number M of thealloy-constituting metal.

Example 3

Al and B employed as a substituent for Al were weighed to give a molarratio of Al:B of (1-γ):γ. Then the procedure of Example 2 was repeatedto thereby give alloys Ca(Al₁₋γ B.sub.γ)₂, i.e., CaAl₁.4 B₀.6, CaAl₁.8B₀.2 and CaAl₁.9 B₀.1. These samples were evaluated in the same manneras the one of Example 1. The results of XRD and the determination of thep-c-T characteristics of CaAl₁.8 B₀.2 and CaAl₁.9 B₀.1 are shown inTables 1 and 2, FIG. 3 and FIGS. 6 (a) and (b). The results of DTA ofCaAl₁.6 B₀.2 are shown in FIG. 2(a).

Example 4

Al and B employed as a substituent for Al were weighed to give a molarratio of Al:B of (1-γ):γ and melted to thereby give an alloy. Next, Caand Mg were weighed to give a molar ratio of Ca:Mg of (1-α):α and themixed metal pieces and the above-mentioned alloy Al₁₋γ B.sub.γ (alloy D)were weighed to give a molar ratio of (Ca+Mg):alloy D of 1:2. Then theprocedure of Example 1 was repeated to thereby give alloys Ca₁₋αMg.sub.α (Al₁₋γ B.sub.γ)₂, i.e., Ca₀.9 Mg₀.1 Al₁.9 B₀.1 and Ca₀.9 Mg₀.1Al₁.8 B₀.2. These samples were evaluated in the same manner as the oneof Example 1. The results of XRD and the determination of the p-c-Tcharacteristics of Ca₀.9 Mg₀.1 Al₁.9 B₀.1 are shown in FIG. 4 and Table2. The results of DTA of Ca₀.9 Mg₀.1 Al₁.8 B₀.2 are shown in FIGS. 2 (a)and (b).

Example 5

Al and B and Si, each employed as a substituent for Al, were weighed togive a molar ratio of Al:B:Si of (1-ε-ζ):ε:ζ (wherein 0≦(ε+ζ)≦0.3) andmelted to thereby give an alloy. Next, the resulting alloy Al₁₋ε-ζB.sub.ε Si.sub.ζ (alloy E) and Ca were weighed to give a molar ratio ofCa:alloy E of 1:2. Then the procedure of Example 1 was repeated tothereby give Ca(Al₁₋ε-ζ B.sub.ε Si.sub.ζ)₂ alloys, i.e., CaAl₁.8 B₀.1Si₀.1 and CaAl₁.9 B₀.05 Si₀.05. These samples were evaluated in the samemanner as the one of Example 1. The results of XRD of CaAl₁.8 B₀.1 Si₀.1and CaAl₁.9 B₀.05 Si₀.05 are shown in FIG. 4. The results of DTA ofCaAl₁.8 B₀.1 Si₀.1 are shown in FIGS. 2(a) and (b).

As described above, the calcium-aluminum system hydrogen absorbing alloyof the present invention, which is composed of a Ca base material and anAl base alloy at a specific molar ratio and has a Laves phase with theC15-type structure, has practically usable hydrogen absorptioncharacteristics and is excellent in lightness and cheapness. Moreparticularly speaking, the following effects can be achieved thereby.

(1) Because it comprises light metal elements such as Ca and Al as themain materials, the calcium-aluminum system hydrogen absorbing alloy ofthe present invention has a lower molecular weight than others (see, forexample, Table 1). Namely, the alloy per se is a light one compared withthe conventional hydrogen absorbing alloys.

                  TABLE 2                                                         ______________________________________                                                              Hydrogen  Equilibrium                                            Chemical     storage   hydrogen                                               formula of   capacity  dissociation                                  Ex. no.  alloy        (M/M)     pressure (MPa)                                ______________________________________                                        1        CaAl.sub.2   0.09      0.11 (0° C.)                           2        CaAl.sub.1.8 Sn.sub.0.2                                                                    0.12      0.05 (0° C.)                           3        CaAl.sub.1.8 B.sub.0.2                                                                     0.24      0.10 (60° C.)                                   CaAl.sub.1.4 B.sub.0.6                                                                     0.19      0.09 (60° C.)                          4        Ca.sub.0.9 Mg.sub.0.1 Al.sub.1.9 B.sub.0.1                                                 0.21      0.13 (60° C.)                          5        CaAl.sub.1.8 B.sub.0.1 Si.sub.0.1                                                          0.25      0.10 (60° C.)                                   CaAl.sub.1.9 B.sub.0.05 Si.sub.0.05                                                        0.12      0.13 (60° C.)                          ______________________________________                                         Note: hydrogen absorption characteristics of the alloy Ca.sub.1-α       Mg.sub.α (Al.sub.1-βM.sub.β).sub.σ of each Example.

(2) The calcium-aluminum system hydrogen absorbing alloys of the presentinvention enable reversible absorption and desorption of hydrogen atordinary temperatures under relatively ordinary hydrogen pressures.

(3) As Table 3 shows, the raw materials for the alloy (Ca, Al, etc.)occur in a large amount as natural resources and can be supplied at alow price, which makes the calcium-aluminum system hydrogen absorbingalloy highly advantageous from the viewpoint of cost. Moreover, the costof the calcium-aluminum system hydrogen absorbing alloy of the presentinvention can be further cut down via mass production. That is to say,it is suitable for the production on an industrial scale.

                  TABLE 3                                                         ______________________________________                                                           Occurrence Price Price                                     Element                                                                              Atomic weight                                                                             (g/ton)    (yen/kg)                                                                            (10.sup.3 yen/mol)                        ______________________________________                                        Ca     40.08       36,300     1,500 60.1                                      Al     26.982      81,300     170   4.6                                       B      10.82       3          9,500 102.8                                     Mg     24.32       20,900     550   13.4                                      Ti     47.90       4,400      1,100 52.6                                      Fe     55.847      50,000     50    2.8                                       Ni     58.71       80         900   52.8                                      Zr     91.22       220        7,000 638.5                                     La     138.91      18.5       23,300                                                                              3,236.6                                   ______________________________________                                         Note: major raw materials of hydrogen absorbing alloy and occurrence and      price thereof.  Reference: the Latest Periodic Table by AGNE (1989)           (occurrence), and Kogyo Rea Metaru (Industrial Rare Metals), 107 (1993),      26 (price)!.                                                             

The alloy according to the present invention, which has thecharacteristics as described above, is useful particularly as a materialfor storing and transporting hydrogen, for conserving heat, etc.

What is claimed is:
 1. Ca--Al system hydrogen absorbing alloy consistingessentially of a mixture P of Ca with Mg represented by the generalformula, (1-α)Ca+αMg (providing 0≦α≦0.2) and an Al base alloy Qrepresented by the general formula, Al₁₋β B.sub.β (providing 0≦β≦0.3),wherein the element M means at least one element selected from the groupconsisting of carbon, silicon, germanium, tin, lead, titanium, vanadium,chromium, manganese, iron, cobalt, nickel, copper and zinc and which hasa molar ratio of P:Q=1:1.5 to 2.8 and a fundamental structure of a Lavesphase with C15 structure.